The response of entangled polymer solutions to step changes of shear rate: Signatures of segmental stretch?

Experiments measuring the orientation angle and birefringence in startup and double-step strain rate flows were conducted on a 3.0 wt % 8.42 × 10⁶ molecular weight polystyrene solution in a Couette flow cell. A phase-modulated flow birefringence apparatus was used to noninvasively probe the sample. Upon startup from rest, the orientation angle undershoots its final steady-state value, as seen by earlier investigators. When the shear rate undergoes a step increase from one nonzero value to another, the amplitude of this undershoot is decreased. However, a more significant effect is a shorter time scale overshoot in the orientation angle that is highly counterintuitive in the sense that an increase of shear rate initially produces a rotation of chain segments away from the flow direction. Similarly, a step decrease in shear rate yields an initial transient rotation toward the flow direction. In both cases, the height of the peaks depends upon the magnitude of the shear rate jump, and the width of the peaks is a function of the final shear rate. The longer time transients in the startup and step increase experiments reflect an apparent change in the relaxation time for segment orientation, which we tentatively attribute to a combination of tube dilation and convective constraint release. The shorter time scale over- and undershoots in the orientation angle appear to be qualitatively explained by considering the differences in extension or contraction of segments along the polymer chain. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36 : 265–280, 1998     

磁场对铁氰化钾与抗坏血酸反应速率的影响

科学实验表明,磁场能改变水系及非水体系的许多物理化学性质,这不仅导致越来越多的科学的工作者对相关的理论问题进行了广泛和深入的研究^[1-4],而且还产生了一系列磁应用技术。从60年代至今,磁场及磁处理技术已在工业、农业、石油开采、混凝土、生物等领域得到了广泛应用^[5-8]。因磁场能改变水及水系的物理化学性质,如果对水系中进行的同一反应,磁场能改变其溶剂效应,则必然引进化学反应速率的改变。基于这种思想,前文^[9,10]曾采用磁处理反应液及磁场直接作用反应体系的方法对水溶液中进行的乙酸乙酯皂化反应体系的方法对水溶液中进行的乙酸乙酯皂化反应的速率常数进行了研究。结果表明,在最佳磁处理和最佳磁场条件下,该反应的速率常数都明显增大。铁氰化钾被抗坏血酸还原也是一个在水溶液中进行的而且其机理研究也较为成熟的反应。本文将采用磁场直接作用于反应体系的方法,研究不同的磁场条件对该反应速率常数的影响。     

Rheological properties of poly(ethylene glycol) solutions and gels

By the interaction of a water–glycol solution of poly(ethylene glycol) (PEG) with calcium chloride dihydrate, a gel was produced. It was determined that, below a certain shear rate, this gel is a Newtonian fluid; however, above a certain shear rate, which depends on the gel viscosity, the properties of this gel are anomalous: the gel flow instantaneously completely stops. The viscosity of the gels was found to exponentially increase with increasing concentration of the cross-linking metal at constant PEG concentration. The density of the gels linearly increases with increasing concentration of the cross-linking metal at constant PEG concentration.     

The form of the rate constant for elementary reactions at equilibrium from MD: framework and proposals for thermokinetics

The rates of formation and concentration distributions of a dimer reaction showing hysteresis behavior are examined in an ab initio chemical reaction designed as elementary and where the hysteresis structure precludes the formation of transition states (TS) with pre-equilibrium and internal sub-reactions. It was discovered that the the reactivity coefficients, defined as a measure of departure from the zero density rate constant for the forward and backward steps had a ratio that was equal to the activity coefficient ratio for the product and reactant species. This surprising result, never formally incorporated in elementary rate expressions over approximately one and a half centuries of quantitative chemical kinetics measurement and calculation is accepted axiomatically and leads to an outline of a theory for the form of the rate constant, in any one given substrate—here the vacuum state. A major deduction is that the long-standing definition of the rate constant for elementary reactions is not complete and is nonlinear, where previous works almost always implicitly refer to the zero density limit for strictly irreducible elementary reactions without any attending concatenation of side-reactions. This is shown directly from MD simulation, where for specially designed elementary reactions without any transition states, density dependence of reactants and products always feature, in contrast to current practice of writing rate equations. It is argued that the rate constant expression without reactant and product dependence is due to historical conventions used for strictly elementary reactions. From the above observations, a theory is developed with the aid of some proven elementary theorems in thermodynamics, and expressions under different state conditions are derived whereby a feasible experimental and computational method for determining the activity coefficients from the rate constants may be obtained under various approximations and conditions. Elementary relations for subspecies equilibria and its relation to the bulk activity coefficient are discussed. From one choice of reaction conditions, estimates of activity coefficients are given which are in at least semi-quantitative agreement with the data for non-reacting Lennard-Jones (LJ) particles for the atomic component. The theory developed is applied to ionic reactions where the standard Brönsted-Bjerrum rate equation and exceptions to this are rationalized.     

注塑成型充填过程中注射速率的优化设计

给出一种塑料注射成型工艺的优化方法 .将充填过程数值模拟和优化算法相结合 ,以获得均匀熔体前沿速度从而减少塑件翘曲变形为目标 ,对充填过程中的注射速率进行优化 .算例表明 ,本文所提出的工艺优化模型及求解算法是有效的     

含蜡原油胶凝过程特性研究

利用RS75流变仪在小振幅振荡剪切的模式下分别研究了3种不同历史条件下含蜡原油的胶凝过程, 同时通过偏光显微镜观察了不同降温速率条件下原油中的蜡晶形貌. 结果表明, 在静态降温条件下, 降温速率越大, 原油胶凝的温度越低, 原油形成的胶凝结构越弱; 并且降温速率越大, 原油在恒温静止过程中, 结构随时间恢复的速率越大, 恢复至平衡所需时间越长, 但最终的平衡结构却越弱; 在同样的降温速率下, 原油低温胶凝结构随着降温过程中剪切作用的增强而减弱, 但当历史剪切速率超过一定数值时, 原油的胶凝结构将基本不再继续变化; 在同样的历史剪切速率下, 降温速率越大, 原油在低温(31 ℃)静止初始的储能模量越小, 但最终的平衡结构却越强.     

纳米氧化铜的粒度对多相反应动力学参数的影响

本文提出了纳米体系多相反应动力学活化能的模型，并以纳米氧化铜与硫酸氢钠溶液的反应为体系，研究了反应物粒度对动力学参数的影响规律，讨论了表观活化能降低的原因。结果表明：反应物粒度对多相反应的反应级数、速率常数、表观活化能和指前因子均有较大的影响；随着反应物粒径的减小，表观活化能和指前因子减小,而反应级数和速率常数增大，并且速率常数和表观活化能与反应物粒径的倒数呈线性关系；这些影响规律与理论模型是一致的。另外，还发现反应物粒度是通过摩尔表面积、摩尔表面能和摩尔表面熵影响多相反应的动力学参数的。     

Multiaxial ratcheting behavior of PTFE at room temperature

A series of multiaxial ratcheting experiments have been performed on polyteterafluoroethylene (PTFE) solid cylindrical specimens. All the tests were conducted under cyclic shear strain with a constant axial stress at room temperature. The effects of axial stress, shear strain range, shear strain rate and their histories on the ratcheting behavior of PTFE were studied. It is shown that the ratcheting strain depends on the constant axial stress, cyclic shear strain range and shear strain rate. The ratcheting strain increases more rapidly as the constant axial stress or shear strain range become larger, or the shear strain rate is reduced. Furthermore, the loading histories also play an important role in the progress of ratcheting. The prior cycling with higher axial stress, larger strain range or lower strain rate greatly restrains ratcheting strain of subsequent cycling at lower strains. Such phenomenon is due to the enhancement of the material deformation resistance caused by the prior loadings.     

二级反应速率常数与活化能计算问题的讨论

In this paper, we discussed several problems on calculation of reaction rate constant in physical chemistry reference books. When calculating the rate constant k of the second-order reaction, we should make the half-life formula consistent with the reaction stoichiometric equation. And when calculating the activation energy with Arrhenius formula for ideal gas-phase reaction, attention should be paid to identifying the difference between the reaction rate constant k_c and k_p, as well as the difference between corresponding activation energy E_ac and E_ap. It is beneficial for students to have a correct understanding in calculation.     

含铋配合物与奈瑟氏菌铁结合蛋白的反应性质研究

铁结合蛋白(Fbp)是致病菌获取Fe3+的关键蛋白。本文采用氨三乙酸(H3NTA)和硝酸铋反应制备BiNTA.2H2O,并运用元素分析、NMR等手段进行表征。通过在大肠杆菌中克隆表达和分离纯化出奈瑟氏淋病双球菌的Fbp,测定不同计量比nBiNTA/napo-Fbp下反应的紫外可见光谱,确定BiNTA与apo-Fbp的反应为一级反应,反应速率常数约为(0.175±0.064)min-1(10 mmol.L-1 Hepes/HPO42-pH 7.4缓冲溶液,310 K)。NH4BiCit与apo-Fbp的反应也为一级反应,反应速率与BiNTA相近。Bi3+与apo-Fbp的饱和结合计量比为1∶1,形成三元配合物Fbp-Bi-NTA的结合常数(lgK)为(21.43±0.20),形成Fbp-Bi-Cit的结合常数(lgK)为(16.03±0.03)。实验结果表明,致病菌中运输Fe3+的蛋白铁结合蛋白可作为含铋抗菌药物的潜在靶分子。     

建立反应速率方程的新方法

对于有一定级数的反应,不论反应级数是几,建立反应速率方程时都可以用非线性拟合法来完成。该方法分为两步。第一步,初次对实验数据进行非线性拟合,从而得到反应级数;第二步,借助已得到的反应级数再次对实验数据进行非线性拟合,从而得到反应速率常数。与传统建立反应速率方程的方法相比较,非线性拟合法不仅简单易操作,而且处理结果准确、图线美观大方。     

A novel dynamic constitutive micromechanical model to predict the strain rate dependent mechanical behavior of glass/epoxy laminated composites

In the present research, a novel dynamic constitutive micromechanical (DCM) model was developed to predict the strain rate dependent mechanical behavior of laminated glass/epoxy composites. The present model is an integration of the generalized strain rate dependent constitutive model as a constitutive model for the neat polymer, the plasticity model of Huang as a micromechanical model, and dynamic progressive failure criteria. This model is able to predict the longitudinal and transverse tensile and in-plane shear behaviors of unidirectional glass/epoxy composites with arbitrary fiber volume fractions at arbitrary strain rates. The present model can also predict the stress-strain behavior of laminated composites with different layups and fiber volume fractions at arbitrary strain rates. A comparison between the results predicted by the present model and the available experimental data showed that the model predicts the strain rate dependent mechanical behavior of glass/epoxy composites with very good accuracy.     

The integration of an ultraviolet-visible spectrometer and a reaction calorimeter

A small ultraviolet-visible absorption spectrometer which uses fibre optic coupled immersion probes has been incorporated into a laboratory scale reaction calorimeter. The combined instrument has been tried out using the hydrolysis of acetic anhydride as a test reaction. With the calorimeter operating in the isoperibolic mode good agreement is found for the pseudo-first order reaction rate constant as determined from spectroscopic and calorimetric measurements. Experiments have been made in order to follow the reaction indirectly using optical pH measurements with acid-base indicators. The possibility of determining the temperature dependence of the rate constant in a single experiment has also been investigated. This revised version was published online in July 2006 with corrections to the Cover Date.     

微波处理后石油焦水蒸气气化特性的研究

采用热天平考察了1 000~1 150 ℃、30%~100%水蒸气分压下微波处理后石油焦气化动力学特性,并采用四种动力学模型对气化反应速率曲线进行了拟合。结果表明,微波处理后石油焦水蒸气气化反应速率随着微波照射时间、功率、温度的减小而增加,随着水蒸气分压的增加而增加;微波处理后石油焦在1 100 ℃时水蒸气气化反应速率随着转化率的增加先增加后减小,在转化率为20%左右出现最大值,且不随微波处理条件和水蒸气分压的变化而改变,但随着气化温度的升高气化反应速率最大值提前出现。正态分布函数模型能够准确的拟合不同温度下微波处理后石油焦水蒸气气化反应速率随转化率的变化,相关系数均在0.97以上。     

Strukturviskosität von verdünnten Lösungen von Biopolymeren

The importance of the rheological behaviour of solutions of macromolecules is briefly evaluated. The viscosity of the solutions depends on concentration, shear rate and time of shear, this relation being determined by the structure of the dissolved molecules. In dilute solutions shear dependence of viscosity is very frequently caused by the preferential orientation of anisotropic molecules. In such a case the particle dimensions can be calculated from the true limiting viscosity number, an anisotropy factor, the rotational diffusion constant and the effective particle density. These numbers can be derived from the flow curve, which has been extrapolated to zero concentration. It is necessary to measure the flow curve at shear gradients, which are sufficiently low to allow for an extrapolation to vanishing shear rate. By comparing the experimental flow curve with a choice of theoretical ones, the rotational diffusion constant and the anisotropy factor (axial ratio) can be found. From the limiting viscosity number and the axial ratio, the particle density can be calculated.     

Shear influence on the phase behavior of systems containing a homopolymer A and a block copolymer AB

Cloud point temperatures (T_cp) and crystallization temperatures (T_l/s) of the ternary system tetrahydronaphthalene/poly(ethylene oxide)/poly(dimethyl siloxane-b-ethylene oxide) have been measured at different constant shear rates using a rheo-optical device and an advanced rheometer. The cloud points temperatures (UCST-type phase diagram) are reduced by several degrees as the system flows; i.e. the shear can suppress the phase separation and enlarge the homogenous region. The crystallization kinetics of PEO in the ternary mixtures has been investigated isothermally and non-isothermally at quiescent state and under shear. The shear could strongly enhance the crystallization i.e. the (T_l/s) shifts to higher temperatures and the induction time, t₀ (the time needs for the onset of crystallization) substantially decreases with increasing shear rate during the non-isothermal and isothermal crystallization processes, respectively. The isothermal crystallization kinetics at quiescent state and at different shear rates was analyzed on the bases of Avrami approach. The Avrami exponent which provides qualitative information about the nature of the nucleation and growth process, was found to be shear rate and temperature dependent. The Avrami exponent increased from ∼3 at the quiescent state to as large as 9 at &&ggr;dot; = 100 s⁻¹.     

Algorithm to evaluate rate constants for polyatomic chemical reactions. II. Applications

A new implementation of the classical reaction path-Liouville algorithm, as developed by the authors in the preceding paper, is tested with several chemical reactions. It results in a simple algorithm, which may be used straightforwardly for the calculation of rate constants, as well as to extract dynamical information of the reactive process. Results for the rate constant have been compared to transition state calculations, confirming that it provides a new lower bound than traditional transition state estimates. In addition, the time-dependence of the kinetic energy stored in vibrational modes has been studied, as a means of characterizing the importance of each normal mode inside the reaction mechanism.     

微乳液体系中过硫酸钾氧化碘离子的动力学研究

分别在不同盐浓度的自由水和不同液滴尺寸的微乳液中测量了过硫酸钾氧化碘 离子的化学反应速率常数，获得微乳液不核中水的活度，探讨了水的活度及体系中 离子强度与反应速率的关系，发现当表面活性剂与水的摩尔比R≤20时，水的活度 随微反应器尺寸减小而快速下降。     

氯化聚氯乙烯/氯化聚乙烯共混体的流变性能

<正> 氯化聚氯乙烯(CPVC)是聚氯乙烯(PVC)的氯化产物。它具有优良的耐化学腐蚀、耐油、隔氧等性能。它的使用温度、抗张和弯曲强度与PVC相比有很大提高。这些特性加上氯元素资源丰富、价格便宜,使CPVC可望成为具有吸引力的热塑性工程塑料。有关CPVC共混体系的研究已有不少报道。然而多数的研究范围较窄,尤其是关于CPVC共混体系流变性研究很少见。本文首次广泛研究了不同组成的CPVC/CPE共混     

Transient response of an electrorheological fluid under square-wave electric field excitation

The transient process of an electrorheological (ER) fluid based on zeolite and silicone oil sheared between two parallel plates to which a square-wave electric field is applied has been experimentally studied. The transient shear stress response to the strain or time is tested. The characteristic constants of time under different applied electric fields and shear rates have been determined. The response time is found to be proportional to shear rate with an exponent of about -0.75 in the tested shear rate range, which agrees with the theoretical predictions made by others. But it only shows a small dependence on the strength of the applied electric field. The results show that the transient process of ER fluids is related to the structure formation in the shearing. When the required shear strain is reached, the shear stress rises to a stable value under constant electric field. Although the electric field strength greatly affects the yield strength, it shows little effect on the stress response time. Also, experiments showed the electric field-induced shear stress decreased with an increase of shear rate.